title: Control of asymmetry in the radical addition approach to chiral amine synthesis.
abstract: The state-of-the-science in asymmetric free radical additions to imino compounds is presented, beginning with an overview of methods involving stereocontrol by various chiral auxiliary approaches. Chiral N-acylhydrazones are discussed with respect to their use as radical acceptors for Mn-mediated intermolecular additions, from design to scope surveys to applications to biologically active targets. A variety of aldehydes and ketones serve as viable precursors for the chiral hydrazones, and a variety of alkyl iodides may be employed as radical precursors, as discussed in a critical review of the functional group compatibility of the reaction. Applications to amino acid and alkaloid synthesis are presented to illustrate the synthetic potential of these versatile stereocontrolled carbon-carbon bond construction reactions. Asymmetric catalysis is discussed, from seminal work on the stereocontrol of radical addition to imino compounds by non-covalent interactions with stoichiometric amounts of catalysts, to more recent examples demonstrating catalyst turnover.
authors.affiliation: Department of Chemistry, University of Iowa, Iowa City, IA, 52242, USA, gregory-friestad@uiowa.edu.
authors.forename: Gregory K
authors.initials: GK
authors.lastname: Friestad
mesh_terms: D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D006835:Hydrazones / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000588:Amines; D006835:Hydrazones